CN105859273B - A kind of 2-2 type BiFeO3-CuFe2O4 laminated film and preparation method thereof - Google Patents
A kind of 2-2 type BiFeO3-CuFe2O4 laminated film and preparation method thereof Download PDFInfo
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
Abstract
The present invention provides a kind of 2-2 type BiFeO3‑CuFe2O4Laminated film and preparation method thereof first prepares CuFe respectively2O4Precursor liquid and BiFeO3Precursor liquid；Then spin coating prepares multi-layer C uFe on substrate2O4Film, then in CuFe2O4Spin coating prepares multilayer BiFeO on film3Film to get arrive BiFeO3‑CuFe2O4Laminated film.The present invention uses sol-gal process, and the uniformity of film of preparation is good, and chemical constituent controllable precise, by BiFeO3The CuFe of film and ferromagnetism spinel structure2O4Film laminated, obtained BiFeO3‑CuFe2O4The saturation magnetization M of laminated filmsFor 25.8emu/cm3, remanent magnetization MrFor 17.8emu/cm3；Its dielectric loss frequency spectrum occurs meeting Maxwell Wagner directric relaxation simultaneously；There is a resistance hysteresis under forward bias in the leakage current of film.
Description
Technical field
The invention belongs to field of functional materials, and in particular to a kind of 2-2 type BiFeO3-CuFe2O4Laminated film and its preparation
Method.
Background technique
As a kind of typical single phase multi-iron material, the secret (BiFeO of the ferrous acid of pure phase3) there is perovskite structure, it is a small number of
There is one of ferroelectricity and anti-ferromagnetic multi-iron material simultaneously at room temperature, ferroelectrie Curie temperature is 850 DEG C, anti-ferromagnetism
Neel temperature be 370 DEG C.BiFeO3Film has caused more and more researchers as a kind of typical iron store
Concern.Utilize its high dielectric constant and magnetic conductivity, it is possible to high capacitance and big inductor integrated electronic component is made,
For reducing the number of devices on high density circuit board, interfering with each other for perceptual device and capacitive device is solved the problems, such as.Utilize it
Magnetoelectric effect be possible to design the magneto-optic disk of the fast-magnetic reversion induced with quick electric polarization, to replace existing slow
Fast magnetic reading and writing memory material.However BiFeO3The ferromagnetic property of film is weak, hinders BiFeO3The practical application of film.
The film of spinel type ferrite shows many at numerous aspects such as optical property, electrical properties, magnetic property
Novel characteristic.CuFe2O4Belong to spinel type ferrite, be a kind of multifunctional semiconductor material, is a kind of important magnetic material
Material.CuFe2O4Saturation magnetization with higher, high magnetic permeability, big magnetocrystalline anisotropy, big magnetostriction and
High chemical stability.If can be in conjunction with the advantages of both the above material, the multiferroic film that can be had excellent performance, and mesh
It is preceding that there is no the relevant reports of this respect.
Summary of the invention
The purpose of the present invention is to provide a kind of 2-2 type BiFeO3-CuFe2O4Laminated film and preparation method thereof, this method
Using 2-2 type complex form, with BiFeO3As ferroelectric layer, CuFe2O4As magnetosphere, BiFeO can be improved3Ferromagnetism
Energy.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of 2-2 type BiFeO3-CuFe2O4Laminated film, including the upper layer film being combined with each other and lower membrane, wherein on
Tunic is BiFeO3Crystalline state film, lower membrane CuFe2O4Crystalline state film；The BiFeO3Crystalline state film is the perovskite structure of distortion,
Rhombohedral system, space group are R3c:H (161)；CuFe2O4Crystalline state film is tetragonal phase, spinel structure, space group I41/
amd(141)。
Its saturation magnetization MsFor 25.8emu/cm3, remanent magnetization MrFor 17.8emu/cm3；In -200kV/cm
Negative sense electric field bias under, leakage current density be 3.87 × 10-2A/cm2。
A kind of 2-2 type BiFeO3-CuFe2O4The preparation method of laminated film, comprising the following steps:
Step 1, in molar ratio it is that 1:2 is dissolved in ethylene glycol monomethyl ether by copper nitrate and ferric nitrate, adds after mixing evenly
Acetic anhydride obtains CuFe2O4Precursor liquid, CuFe2O4The concentration of Fe ion is 0.1~0.2mol/L in precursor liquid；
Step 2, in molar ratio it is that 1:1 is dissolved in solvent by bismuth nitrate and ferric nitrate, obtains BiFeO3Precursor liquid, wherein
BiFeO3The total concentration of metal ion is 0.003~0.3mol/L in precursor liquid, and solvent is the mixed of ethylene glycol monomethyl ether and acetic anhydride
Close liquid；
Step 3, using spin-coating method on substrate spin coating CuFe2O4Precursor liquid obtains CuFe2O4Wet film, CuFe2O4Wet film is through even
Dry film is toasted to obtain after glue at 250~300 DEG C, is annealed in air at 610~620 DEG C, crystalline state CuFe is obtained2O4Film；
Step 4, to crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated on film, until reaching institute
Thickness is needed, CuFe is obtained2O4Crystalline state film；
Step 5, in CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid obtains BiFeO3Wet film, BiFeO3Wet film is after spin coating
Dry film is toasted to obtain at 220~250 DEG C, is annealed in air at 555~565 DEG C, and crystalline state BiFeO is obtained3Film；
Step 6, to crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Step 5 is repeated on film, until needed for reaching
Thickness obtains 2-2 type BiFeO3-CuFe2O4Laminated film.
The CuFe2O4Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (3.5~4.5) in precursor liquid: 1；The step
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (2.5~3.5) in 2 solvent: 1.
The substrate is FTO/ glass substrate, Si substrate, SrTiO3Monocrystal chip or LaNiO3Monocrystal chip.
The step 3 first cleans substrate before progress, then treatment with irradiation under ultraviolet light, makes substrate surface
Reach atomic cleanliness degree, then spin coating CuFe2O4Precursor liquid；
The step 5 is before progress, first to CuFe2O4Crystalline film carries out ultraviolet light processing, makes CuFe2O4Crystalline state
Film surface reaches atomic cleanliness degree, then spin coating BiFeO3Precursor liquid.
Spin coating revolving speed in the step 3 and step 5 when spin coating is 4200~4500r/min, and spin coating time is 7~10s.
Baking time in the step 3 and step 5 after spin coating is 10~15min.
Annealing time in the step 3 is 25~30min, and the annealing time in step 5 is 8~12min.
The 2-2 type BiFeO3-CuFe2O4Laminated film is by 1~6 layer crystal state CuFe2O4Film and 3~15 layer crystal states
BiFeO3Film is constituted.
Compared with the existing technology, the invention has the following advantages:
1. 2-2 type BiFeO provided by the invention3-CuFe2O4The preparation method of laminated film selects BiFeO3With CuFe2O4
It is compound, this is because CuFe2O4It is ideal magnetic composite with very strong magnetism.By BiFeO3And CuFe2O4Film into
Row 2-2 type is compound, is capable of forming while having the 2-2 type BiFeO of ferroelectric properties and ferromagnetic property3-CuFe2O4Laminated film.
2. currently used for preparing BiFeO3The method of film has very much, such as chemical vapour deposition technique (CVD), magnetron sputtering method
(rf magnetron sputtering), deposition of metal organic method (MOD), metal-organic chemical vapor deposition equipment method
(MOCVD), liquid phase deposition (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel method
(Sol-Gel) etc..Compared to other methods, Sol-Gel method reacts since equipment is simple and is easy to carry out, reaction temperature is lower, easily
Operation, is suitable for preparing film on big surface and surface in irregular shape, the Uniform Doped on Yi Shixian molecular level, with
And the advantages that chemical constituent controllable precise and be widely used for preparing ferroelectric material.It is prepared in the present invention using sol-gal process
BiFeO3Film, and and CuFe2O4Film laminated is prepared for 2-2 type BiFeO on substrate3-CuFe2O4Laminated film, equipment
It is required that simple, experiment condition is easy to reach, the 2-2 type BiFeO of preparation3-CuFe2O4Laminated film uniformity is good, and it is special to have
Leakage current density curve, there is directric relaxation phenomenon in dielectric loss frequency spectrum, and improves BiFeO3Ferromagnetic property.
3. 2-2 type BiFeO provided by the invention3-CuFe2O4Laminated film is by the upper layer film and lower membrane that are combined with each other
It constitutes, wherein upper layer film is BiFeO3Crystalline state film, lower membrane CuFe2O4Crystalline state film；BiFeO3Crystalline state film is the perovskite of distortion
Structure, rhombohedral system, space group are R3c:H (161)；CuFe2O4Crystalline state film is tetragonal phase, and spinel structure, space group is
I41/amd(141)。
Detailed description of the invention
Fig. 1 is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The XRD diagram of laminated film；
Fig. 2 is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The Raman map of laminated film；
Fig. 3 is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The surface SEM of laminated film schemes and section SEM figure；
Fig. 4 is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The dielectric constant and dielectric loss frequency spectrum of laminated film
Figure；
Fig. 5 is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The leakage electrical conduction current of laminated film and the relational graph of electric field；
Fig. 6 (a) is 2-2 type BiFeO prepared by the present invention3-CuFe2O4The ferroelectric hysteresis loop figure of laminated film, Fig. 6 (b) are these
Invent the 2-2 type BiFeO of preparation3-CuFe2O4The hysteresis loop figure of laminated film.
Specific embodiment
The present invention is described in further details below with reference to the present invention preferably embodiment and attached drawing.
Embodiment 1
It step 1, is in molar ratio that 1:2 is dissolved in ethylene glycol monomethyl ether by copper nitrate and ferric nitrate, after stirring 30min, then plus
Enter acetic anhydride, obtains the stable CuFe that Fe ion concentration is 0.1mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol first in precursor liquid
The volume ratio of ether and acetic anhydride is 4:1；
Step 2, in molar ratio it is that 1:1 is dissolved in solvent (bismuth nitrate excessive 5%) by bismuth nitrate and ferric nitrate, obtains metal
Total ion concentration is the stable BiFeO of 0.3mol/L3Precursor liquid；Wherein solvent be volume ratio be 3:1 ethylene glycol monomethyl ether and
The mixed liquor of acetic anhydride；
Step 3, FTO/ glass substrate is sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic wave is clear
It washes after 10min with a large amount of distilled water flushing FTO/ glass substrates, finally with being dried with nitrogen.Then FTO/ glass substrate is put into
Baking oven is baked to drying, takes out and stands to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument again and is irradiated
40min makes FTO/ glass substrate surface reach " atomic cleanliness degree ".Then spin-coating method spin coating in FTO/ glass substrate is used
CuFe2O4Precursor liquid obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating revolving speed are 4200r/min, and spin coating time is
10s after spin coating, toasts 12min at a temperature of 250 DEG C and obtains dry film, then anneal layer by layer in air at a temperature of 620 DEG C
25min obtains crystalline state CuFe2O4Film；
Step 4, to crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated on film, is repeated 2 times, is obtained
To CuFe2O4Crystalline state film；
Step 5, by CuFe2O4Crystalline state film, which is placed in ultraviolet radiation instrument, irradiates 40min, its surface is made to reach atomic cleanliness
Degree；Again in CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating revolving speed
For 4200r/min, spin coating time 10s, after spin coating, 12min is toasted at 220 DEG C and obtains dry film, then the air at 565 DEG C
In anneal layer by layer 10min, obtain crystalline state BiFeO3Film；
Step 6, to crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Step 5 is repeated on film, is repeated 5 times, is obtained
2-2 type BiFeO3-CuFe2O4Laminated film.
Embodiment 2
It step 1, is in molar ratio that 1:2 is dissolved in ethylene glycol monomethyl ether by copper nitrate and ferric nitrate, after stirring 30min, then plus
Enter acetic anhydride, obtains the stable CuFe that Fe ion concentration is 0.14mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol in precursor liquid
The volume ratio of methyl ether and acetic anhydride is 3.5:1；
Step 2, in molar ratio it is that 1:1 is dissolved in solvent (bismuth nitrate excessive 5%) by bismuth nitrate and ferric nitrate, obtains metal
Total ion concentration is the stable BiFeO of 0.003mol/L3Precursor liquid；Wherein solvent is the ethylene glycol first that volume ratio is 2.5:1
The mixed liquor of ether and acetic anhydride；
Step 3, FTO/ glass substrate is sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic wave is clear
It washes after 10min with a large amount of distilled water flushing FTO/ glass substrates, finally with being dried with nitrogen.Then FTO/ glass substrate is put into
Baking oven is baked to drying, takes out and stands to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument again and is irradiated
40min makes FTO/ glass substrate surface reach " atomic cleanliness degree ".Then spin-coating method spin coating in FTO/ glass substrate is used
CuFe2O4Precursor liquid obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating revolving speed are 4300r/min, and spin coating time is
9s after spin coating, toasts 15min at a temperature of 260 DEG C and obtains dry film, then anneal layer by layer in air at a temperature of 610 DEG C
26min obtains crystalline state CuFe2O4Film；
Step 4, to crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated on film, is repeated 5 times, is obtained
To CuFe2O4Crystalline state film；
Step 5, by CuFe2O4Crystalline state film, which is placed in ultraviolet radiation instrument, irradiates 40min, its surface is made to reach atomic cleanliness
Degree；Again in CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating revolving speed
For 4300r/min, spin coating time 9s, after spin coating, 14min is toasted at 230 DEG C and obtains dry film, then the air at 555 DEG C
In anneal layer by layer 12min, obtain crystalline state BiFeO3Film；
Step 6, to crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Step 5 is repeated on film, is repeated 6 times, is obtained
2-2 type BiFeO3-CuFe2O4Laminated film.
Embodiment 3
It step 1, is in molar ratio that 1:2 is dissolved in ethylene glycol monomethyl ether by copper nitrate and ferric nitrate, after stirring 30min, then plus
Enter acetic anhydride, obtains the stable CuFe that Fe ion concentration is 0.2mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol first in precursor liquid
The volume ratio of ether and acetic anhydride is 4.5:1；
Step 2, in molar ratio it is that 1:1 is dissolved in solvent (bismuth nitrate excessive 5%) by bismuth nitrate and ferric nitrate, obtains metal
Total ion concentration is the stable BiFeO of 0.05mol/L3Precursor liquid；Wherein solvent is the ethylene glycol monomethyl ether that volume ratio is 3.5:1
With the mixed liquor of acetic anhydride；
Step 3, FTO/ glass substrate is sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic wave is clear
It washes after 10min with a large amount of distilled water flushing FTO/ glass substrates, finally with being dried with nitrogen.Then FTO/ glass substrate is put into
Baking oven is baked to drying, takes out and stands to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument again and is irradiated
40min makes FTO/ glass substrate surface reach " atomic cleanliness degree ".Then spin-coating method spin coating in FTO/ glass substrate is used
CuFe2O4Precursor liquid obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating revolving speed are 4400r/min, and spin coating time is
8s after spin coating, toasts 14min at a temperature of 270 DEG C and obtains dry film, then anneal layer by layer in air at a temperature of 612 DEG C
27min obtains crystalline state CuFe2O4Film；
Step 4, to crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated on film, is repeated 1 times, is obtained
To CuFe2O4Crystalline state film；
Step 5, by CuFe2O4Crystalline state film, which is placed in ultraviolet radiation instrument, irradiates 40min, its surface is made to reach atomic cleanliness
Degree；Again in CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating revolving speed
For 4400r/min, spin coating time 8s, after spin coating, 11min is toasted at 240 DEG C and obtains dry film, then the air at 560 DEG C
In anneal layer by layer 11min, obtain crystalline state BiFeO3Film；
Step 6, to crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Step 5 is repeated on film, is repeated 8 times, is obtained
2-2 type BiFeO3-CuFe2O4Laminated film.
Embodiment 4
It step 1, is in molar ratio that 1:2 is dissolved in ethylene glycol monomethyl ether by copper nitrate and ferric nitrate, after stirring 30min, then plus
Enter acetic anhydride, obtains the stable CuFe that Fe ion concentration is 0.12mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol in precursor liquid
The volume ratio of methyl ether and acetic anhydride is 3.7:1；
Step 2, in molar ratio it is that 1:1 is dissolved in solvent (bismuth nitrate excessive 5%) by bismuth nitrate and ferric nitrate, obtains metal
Total ion concentration is the stable BiFeO of 0.01mol/L3Precursor liquid；Wherein solvent is the ethylene glycol monomethyl ether that volume ratio is 2.7:1
With the mixed liquor of acetic anhydride；
Step 3, Si substrate is sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic cleaning
With a large amount of distilled water flushing Si substrates after 10min, finally with being dried with nitrogen.Then Si substrate is put into baking oven and is baked to drying,
It takes out and stands to room temperature.Clean Si substrate is placed in ultraviolet radiation instrument again and irradiates 40min, reaches Si substrate surface
" atomic cleanliness degree ".Then spin-coating method spin coating CuFe on si substrates is used2O4Precursor liquid obtains CuFe2O4Wet film, it is right
CuFe2O4Wet film spin coating, spin coating revolving speed are 4500r/min, spin coating time 7s, after spin coating, are toasted at a temperature of 280 DEG C
13min obtains dry film, then the 30min that anneals layer by layer in air at a temperature of 618 DEG C, obtains crystalline state CuFe2O4Film；
Step 4, to crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated on film, is repeated 3 times, is obtained
To CuFe2O4Crystalline state film；
Step 5, by CuFe2O4Crystalline state film, which is placed in ultraviolet radiation instrument, irradiates 40min, its surface is made to reach atomic cleanliness
Degree；Again in CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating revolving speed
For 4500r/min, spin coating time 7s, after spin coating, 10min is toasted at 250 DEG C and obtains dry film, then the air at 558 DEG C
In anneal layer by layer 11.5min, obtain crystalline state BiFeO3Film；
Step 6, to crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Step 5 is repeated on film, is repeated 11 times, is obtained
2-2 type BiFeO3-CuFe2O4Laminated film.
Embodiment 5
It step 1, is in molar ratio that 1:2 is dissolved in ethylene glycol monomethyl ether by copper nitrate and ferric nitrate, after stirring 30min, then plus
Enter acetic anhydride, obtains the stable CuFe that Fe ion concentration is 0.18mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol in precursor liquid
The volume ratio of methyl ether and acetic anhydride is 3.9:1；
Step 2, in molar ratio it is that 1:1 is dissolved in solvent (bismuth nitrate excessive 5%) by bismuth nitrate and ferric nitrate, obtains metal
Total ion concentration is the stable BiFeO of 0.1mol/L3Precursor liquid；Wherein solvent is the ethylene glycol monomethyl ether that volume ratio is 2.9:1
With the mixed liquor of acetic anhydride；
Step 3, by SrTiO3Monocrystal chip is sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic wave
With a large amount of distilled water flushing SrTiO after cleaning 10min3Monocrystal chip, finally with being dried with nitrogen.Then by SrTiO3Monocrystal chip
It is put into baking oven and is baked to drying, take out and stand to room temperature.Again by clean SrTiO3Monocrystal chip is placed in ultraviolet radiation instrument
40min is irradiated, SrTiO is made3Monocrystal chip surface reaches " atomic cleanliness degree ".Then using spin-coating method in SrTiO3Monocrystal chip
Upper spin coating CuFe2O4Precursor liquid obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating revolving speed are 4350r/min, spin coating
Time is 8.5s, after spin coating, at a temperature of 290 DEG C toast 11min obtain dry film, then at a temperature of 616 DEG C in air layer by layer
Anneal 29min, obtains crystalline state CuFe2O4Film；
Step 4, to crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated on film, is repeated 4 times, is obtained
To CuFe2O4Crystalline state film；
Step 5, by CuFe2O4Crystalline state film, which is placed in ultraviolet radiation instrument, irradiates 40min, its surface is made to reach atomic cleanliness
Degree；Again in CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating revolving speed
For 4350r/min, spin coating time 8.5s, after spin coating, 15min is toasted at 225 DEG C and obtains dry film, then the sky at 562 DEG C
Anneal 9min layer by layer in gas, obtains crystalline state BiFeO3Film；
Step 6, to crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Step 5 is repeated on film, is repeated 14 times, is obtained
2-2 type BiFeO3-CuFe2O4Laminated film.
Embodiment 6
It step 1, is in molar ratio that 1:2 is dissolved in ethylene glycol monomethyl ether by copper nitrate and ferric nitrate, after stirring 30min, then plus
Enter acetic anhydride, obtains the stable CuFe that Fe ion concentration is 0.16mol/L2O4Precursor liquid, CuFe2O4Ethylene glycol in precursor liquid
The volume ratio of methyl ether and acetic anhydride is 4.2:1；
Step 2, in molar ratio it is that 1:1 is dissolved in solvent (bismuth nitrate excessive 5%) by bismuth nitrate and ferric nitrate, obtains metal
Total ion concentration is the stable BiFeO of 0.2mol/L3Precursor liquid；Wherein solvent is the ethylene glycol monomethyl ether that volume ratio is 3.2:1
With the mixed liquor of acetic anhydride；
Step 3, by LaNiO3Monocrystal chip is sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic wave
With a large amount of distilled water flushing LaNiO after cleaning 10min3Monocrystal chip, finally with being dried with nitrogen.Then by LaNiO3Monocrystal chip
It is put into baking oven and is baked to drying, take out and stand to room temperature.Again by clean LaNiO3Monocrystal chip is placed in ultraviolet radiation instrument
40min is irradiated, LaNiO is made3Monocrystal chip surface reaches " atomic cleanliness degree ".Then using spin-coating method in LaNiO3Monocrystal chip
Upper spin coating CuFe2O4Precursor liquid obtains CuFe2O4Wet film, to CuFe2O4Wet film spin coating, spin coating revolving speed are 4250r/min, spin coating
Time is 7.5s, after spin coating, at a temperature of 300 DEG C toast 10min obtain dry film, then at a temperature of 614 DEG C in air layer by layer
Anneal 28min, obtains CuFe2O4Crystalline state film；
Step 4, by CuFe2O4Crystalline state film, which is placed in ultraviolet radiation instrument, irradiates 40min, its surface is made to reach atomic cleanliness
Degree；Again in CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid obtains BiFeO3Wet film, to BiFeO3Wet film spin coating, spin coating revolving speed
For 4250r/min, spin coating time 7.5s, after spin coating, 13min is toasted at 235 DEG C and obtains dry film, then the sky at 563 DEG C
Anneal 8min layer by layer in gas, obtains crystalline state BiFeO3Film；
Step 5, to crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Step 5 is repeated on film, is repeated 2 times, is obtained
2-2 type BiFeO3-CuFe2O4Laminated film.
Using XRD determining 2-2 type BiFeO produced by the present invention3-CuFe2O4The object phase composition structure of laminated film, uses FE-
SEM measures 2-2 type BiFeO produced by the present invention3-CuFe2O4The microscopic appearance interfacial contact situation of laminated film, uses TF2000
Ferroelectricity test system and test 2-2 type BiFeO produced by the present invention3-CuFe2O4The ferroelectric properties of laminated film, uses Agilent
E4980A precision LCR table tests 2-2 type BiFeO produced by the present invention3-CuFe2O4The dielectric properties of laminated film are used
Agilent B2900 tests 2-2 type BiFeO produced by the present invention3-CuFe2O4The leakage conduction properties of flow of laminated film is used
SQUID MPMS-XL-7 tests 2-2 type BiFeO produced by the present invention3-CuFe2O4The ferromagnetic property of laminated film at room temperature, knot
Fruit is as shown in figures 1 to 6.
As can be known from Fig. 1,2-2 type BiFeO prepared by the present invention3-CuFe2O4Laminated film, 2 θ=22 °, 32 °, 39 °,
46 ° correspond to BiFeO with the diffraction maximum at 56 °3(012), (104) and (110), (006) and (202), (024), (018) and
(300) characteristic peak (JCPDS No.86-1518) of crystal face, shows BiFeO3Perovskite structure with distortion, rhombohedral system,
Space group is R3c:H (161), while can also observe diffraction maximum at 2 θ=18.3 °, 30.5 °, 34.7 ° and 37.1 °, point
Not corresponding is CuFe2O4(100), (200), (103) and (202) crystal face characteristic peak (JCPDS No.34-0425), this table
Bright CuFe2O4Film is spinel structure, tetragonal phase, space group I41/ amd (141) does not have going out for other impurities in film
It is existing.
Fig. 2 is in 141,171,218 and 260cm simultaneously-1The vibration mould at place corresponds to BiFeO3A1-1、A1-2、A1- 3 and E-3
Mould is vibrated, in 496 and 701cm-1Place has faint vibration mould to correspond to CuFe2O4T2gAnd A1gMould is vibrated, is further demonstrated
Film produced by the present invention is BiFeO3-CuFe2O4Laminated film.
2-2 type BiFeO produced by the present invention as can be seen from Figure 33-CuFe2O4Film surface is smooth, and crystal grain is uniform, whole
Body thickness is 540nm, wherein BiFeO3Layer with a thickness of 360nm, CuFe2O4Layer with a thickness of 180nm.
Fig. 4 is 2-2 type BiFeO produced by the present invention3-CuFe2O4The dielectric and magnetic figure of laminated film, wherein BiFeO3-
CuFe2O4It is abbreviated as BFO-CuFO, BiFeO3It is abbreviated as BFO, CuFe2O4It is abbreviated as CuFO.From fig. 4, it can be seen that system of the present invention
The 2-2 type BiFeO obtained3-CuFe2O4Laminated film shows apparent dielectric dispersion phenomenon, and dielectric loss is 10kHz in frequency
When there is dielectric loss peak, meet Maxwell Wagner directric relaxation.
As can be seen from Figure 5, under the negative sense electric field bias of -200kV/cm, 2-2 type BiFeO produced by the present invention3-CuFe2O4
The leakage current density of laminated film is 3.87 × 10-2A/cm2, measured leakage current density curve asymmetric under positive back bias voltage,
And there is a resistance hysteresis under forward bias.
Fig. 6 (a) is 2-2 type BiFeO produced by the present invention3-CuFe2O4Laminated film at room temperature, frequency 1kHz, electric field
The ferroelectric hysteresis loop measured when 20V, from Fig. 6 (a) it can be seen that 2-2 type BiFeO produced by the present invention3-CuFe2O4Laminated film obtains
To be cricoid ferroelectric hysteresis loop, 2-2 type BiFeO3-CuFe2O4The ferroelectric properties of laminated film is smaller.
Fig. 6 (b) is the 2-2 type BiFeO obtained at room temperature3-CuFe2O4The hysteresis loop of laminated film, can from Fig. 6 (b)
Know, 2-2 type BiFeO produced by the present invention3-CuFe2O4The saturation magnetization M of laminated films=25.8emu/cm3, remanence
Change intensity Mr=17.8emu/cm3；Illustration in Fig. 6 (b) is BiFeO3The hysteresis loop of film, it can be seen that BiFeO3Film
Saturation magnetization MsFor 0.67emu/cm3, remanent magnetization MrFor only 0.12emu/cm3.2-2 type produced by the present invention
BiFeO3-CuFe2O4The magnetic property of laminated film is BiFeO340 times of film.
Present device requires simply, and experiment condition is easy to reach, 2-2 type BiFeO obtained3-CuFe2O4Laminated film
BiFeO can be increased substantially3The ferromagnetic property of film, while obtaining special leakage current density curve graph.
Above said content is that a further detailed description of the present invention in conjunction with specific preferred embodiments, is not
Whole or unique embodiment, those of ordinary skill in the art are by reading description of the invention to technical solution of the present invention
Any equivalent transformation taken, all are covered by the claims of the invention.
Claims (6)
1. a kind of 2-2 type BiFeO3-CuFe2O4Laminated film, it is characterised in that: including the upper layer film being combined with each other and lower layer
Film, wherein upper layer film is BiFeO3Crystalline state film, lower membrane CuFe2O4Crystalline state film；The BiFeO3Crystalline state film is the calcium of distortion
Perovskite like structure, rhombohedral system, space group are R3c:H (161)；CuFe2O4Crystalline state film is tetragonal phase, spinel structure, spatial point
Group is I41/amd(141)；
Its saturation magnetization MsFor 25.8emu/cm3, remanent magnetization MrFor 17.8emu/cm3；In the negative sense of -200kV/cm
Under electric field bias, leakage current density is 3.87 × 10-2A/cm2；
Leakage current density curve asymmetric under positive back bias voltage, and there is a resistance hysteresis under forward bias.
2. a kind of 2-2 type BiFeO3-CuFe2O4The preparation method of laminated film, which comprises the following steps:
Step 1, in molar ratio it is that 1:2 is dissolved in ethylene glycol monomethyl ether by copper nitrate and ferric nitrate, adds acetic acid after mixing evenly
Acid anhydride obtains CuFe2O4Precursor liquid, CuFe2O4The concentration of Fe ion is 0.1~0.2mol/L in precursor liquid；
Step 2, in molar ratio it is that 1:1 is dissolved in solvent by bismuth nitrate and ferric nitrate, obtains BiFeO3Precursor liquid, wherein BiFeO3
The total concentration of metal ion is 0.003~0.3mol/L in precursor liquid, and solvent is the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride；
Step 3, using spin-coating method on substrate spin coating CuFe2O4Precursor liquid obtains CuFe2O4Wet film, CuFe2O4Wet film is after spin coating
Dry film is toasted to obtain at 250~300 DEG C, is annealed in air at 610~620 DEG C, and annealing time is 25~30min, is obtained
To crystalline state CuFe2O4Film；
Step 4, to crystalline state CuFe2O4After film cooling, in crystalline state CuFe2O4Step 3 is repeated on film, until reaching required thickness
Degree, obtains CuFe2O4Crystalline state film；
Step 5, in CuFe2O4Spin coating BiFeO on crystalline state film3Precursor liquid obtains BiFeO3Wet film, BiFeO3Wet film after spin coating
Dry film is toasted to obtain at 220~250 DEG C, is annealed in air at 555~565 DEG C, and annealing time is 8~12min, obtains crystalline substance
State BiFeO3Film；
Step 6, to crystalline state BiFeO3After film cooling, in crystalline state BiFeO3Step 5 is repeated on film, until reach required thickness,
Obtain 2-2 type BiFeO3-CuFe2O4Laminated film；
Spin coating revolving speed in the step 3 and step 5 when spin coating is 4200~4500r/min, and spin coating time is 7~10s；
Baking time in the step 3 and step 5 after spin coating is 10~15min.
3. 2-2 type BiFeO according to claim 23-CuFe2O4The preparation method of laminated film, it is characterised in that: described
CuFe2O4Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (3.5~4.5) in precursor liquid: 1；Second in the solvent of the step 2
The volume ratio of glycol methyl ether and acetic anhydride is (2.5~3.5): 1.
4. 2-2 type BiFeO according to claim 23-CuFe2O4The preparation method of laminated film, it is characterised in that: described
Substrate be FTO/ glass substrate, Si substrate, SrTiO3Monocrystal chip or LaNiO3Monocrystal chip.
5. 2-2 type BiFeO according to claim 23-CuFe2O4The preparation method of laminated film, it is characterised in that: described
Step 3 first cleans substrate before progress, then treatment with irradiation under ultraviolet light, and substrate surface is made to reach atomic cleanliness
Degree, then spin coating CuFe2O4Precursor liquid；
The step 5 is before progress, first to CuFe2O4Crystalline film carries out ultraviolet light processing, makes CuFe2O4Crystalline state film surface
Reach atomic cleanliness degree, then spin coating BiFeO3Precursor liquid.
6. 2-2 type BiFeO according to claim 23-CuFe2O4The preparation method of laminated film, it is characterised in that: described
2-2 type BiFeO3-CuFe2O4Laminated film is by 1~6 layer crystal state CuFe2O4Film and 3~15 layer crystal state BiFeO3Film structure
At.
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